Fluorochemical urethane composition for treatment of fibrous substrates

ABSTRACT

Fluorochemical urethane compositions comprising one or more fluorochemical urethane compounds, and one or more auxiliary compounds for treatment of a fibrous substrate are described. The fluorochemical compositions are capable of improving one or more of the oil- and/or water repellency, stain- and/or soil repellency and stain and/or soil release properties, with improved durability, of the fibrous substrate treated with the fluorochemical composition.

FIELD OF THE INVENTION

[0001] This invention relates to chemical compositions comprising one ormore fluorochemical urethane compounds, and one or more auxiliarycompounds for treatment of a fibrous substrate. The invention furtherrelates of fluorochemical coating compositions comprising at least onesolvent and the chemical compositions of the present invention. Thefluorochemical compositions are capable of improving one or more of theoil- and/or water repellency, stain- and/or soil repellency and stainand/or soil release properties, with improved durability, to the fibroussubstrate treated with the fluorochemical composition. This inventionalso relates to articles comprising a fibrous substrate and on thissubstrate is a cured coating derived from the coating compositions ofthe present invention. The cured coating resists being worn-off due towear, abrasion and cleaning. In another aspect, this invention relatesto a process for imparting stain-release characteristics to substrates.

BACKGROUND OF THE INVENTION

[0002] The use of certain fluorochemical compositions on fibers andfibrous substrates, such as textiles, paper, and leather, to impart oil-and water-repellency and soil- and stain-resistance is well known in theart. See, for example, Banks, Ed., Organofluorine Chemicals and TheirIndustrial Applications, Ellis Horwood Ltd., Chichester, England, 1979,pp. 226-234. Such fluorochemical compositions include, for example,fluorochemical guanidines (U.S. Pat. No. 4,540,497, Chang et al.),compositions of cationic and non-cationic fluorochemicals (U.S. Pat. No.4,566,981, Howells), compositions containing fluorochemical carboxylicacid and epoxidic cationic resin (U.S. Pat. No. 4,426,466, Schwartz),fluoroaliphatic carbodiimides (U.S. Pat. No. 4,215,205, Landucci),fluoroaliphatic alcohols (U.S. Pat. No. 4,468,527, Patel),fluorine-containing addition polymers, copolymers, and macromers (U.S.Pat. Nos. 2,803,615; 3,068,187; 3,102,103; 3,341,497; 3,574,791;3,916,053; 4,529,658; 5,216,097; 5,276,175; 5,725,789; 6,037,429),fluorine-containing phosphate esters (U.S. Pat. Nos. 3,094,547;5,414,102; 5,424,474), fluorine-containing urethanes (U.S. Pat. Nos.3,987,182; 3,987,227; 4,504,401; 4,958,039), fluorochemical allophanates(U.S. Pat. Nos. 4,606,737) fluorochemical biurets (U.S. Pat. Nos.4,668,406), fluorochemical oxazolidinones (U.S. Pat. No. 5,025,052), andfluorochemical piperazines (U.S. Pat. No. 5,451,622).

[0003] As indicated above, both solvent and water based fluorochemicalcompositions have been used to provide water- and oil-repellency tofibrous surfaces. Since organic solvents pose health, safety, andenvironmental concerns, the water-based compositions are particularlydesirable. However, the previously known compositions are typicallyaqueous dispersions or emulsions, not solutions; therefore, may requirea high temperature cure to impart good repellency properties. In manycases, for example, high temperature curing is not practical orpossible. For this reason there is a continuing need for urethanes thatdo not require costly and energy consuming high temperature cureconditions to impart good repellency properties. Therefore, urethanecompositions, including those containing fluorine, that displayincreased water solubility are needed to eliminate the need for hightemperature cure conditions, as well as to increase the ease ofpreparation and to provide more stable aqueous solutions.

SUMMARY OF THE INVENTION

[0004] The inventors recognized the need for fluorochemical compositionsthat can successfully impart one or more of the following uniform,durable properties: oil- and water-repellency and/or soil- andstain-resistance and/or soil- and stain-repellency. These chemicalcompositions may be water and/or organic solvent soluble and may notrequire high temperatures for curing.

[0005] In one aspect, this invention relates to chemical compositionscomprising one or more fluorochemical urethane compounds, and one ormore auxiliary compounds capable of further improving the soil- and/orstain release and oil- and/or water repellency of a fibrous substrate.These urethane compounds comprise the reaction product of (a) one ormore polyfunctional isocyanate compounds; (b) one or more hydrophilicpolyoxyalkylene compounds; (c) one or more fluorochemical monofunctionalcompounds; and (d) one or more isocyanate-reactive silanes.

[0006] As used herein, the term “fluorochemical urethane compound” meansa compound derived or derivable from the reaction of at least onepolyfunctional isocyanate compound and at least one hydrophilicpolyoxyalkylene compound, one or more fluorinated monofunctionalcompounds; and (ii) one or more isocyanate-reactive silane compounds.

[0007] The chemical compositions of the present invention, comprisingone or more urethane compounds, impart one or more of release,repellency and resistance characteristics to oil, water, stains andsoils, and exhibit durability (i.e. they resist being worn-off) whenexposed to wear and abrasion from use, cleaning, and the elements.Therefore, these compositions can be applied as coatings to a widevariety of substrates, for example, by topical application, to impartdurable release/repellency/resistant properties to the substrates. Whenapplied as a coating, the chemical compositions of the present inventioncan provide uniform properties to a fibrous substrate and do not changethe appearance of the substrate to which they are applied. Even thoughthe urethane compounds are of relatively low fluorochemical content, thechemical compositions of the present invention provide durablestain-release properties comparable to or better than those of the priorart. In addition, with some embodiments, the chemical compositions ofthe present invention do not require high temperature curing; they canbe cured (i.e., dried) at ambient temperature.

[0008] Certain preferred embodiments of the chemical compositions of thepresent invention include those compositions comprising terminalfluorochemical groups having from two to twelve carbons, preferably fromthree to six carbons, and more preferably four carbons. Even with R_(f)groups that are relatively short (i.e. six or fewer carbons), thesechemical compositions, surprisingly, exhibit excellentrelease/resistance/repellency. Although compositions comprising lowerfluorine content are less expensive, those of skill in the art havetypically overlooked R_(f) groups shorter than eight carbons becausethey have been known to impart inferior oil- and water-repellency andstain resistance.

[0009] Many previously known fluorochemical surfactants containperfluorooctyl moieties. These surfactants ultimately degrade toperfluorooctyl-containing compounds. It has been reported that certainperfluorooctyl-containing compounds may tend to bio-accumulate in livingorganisms; this tendency has been cited as a potential concern regardingsome fluorochemical compounds. For example, see U.S. Pat. No. 5,688,884(Baker et al.). As a result, there is a desire for fluorine-containingcompositions which are effective in providing desiredrelease/resistance/repellency properties, and which eliminate moreeffectively from the body (including the tendency of the composition andits degradation products).

[0010] It is expected that the preferred fluorochemical compositions ofthe present invention, which contain perfluoroalkyl C₃ to C₆ moieties,when exposed to biologic, thermal, oxidative, hydrolytic, and photolyticconditions found in the environment, will break down to variousdegradation products. For example, compositions comprisingperfluorobutylsulfonamido moieties are expected to degrade, at least tosome extent, ultimately to perfluorobutylsulfonate salts. It has beensurprisingly found that perfluorobutylsulfonate, tested in the form ofits potassium salt, eliminates from the body much more effectively thanperfluorohexylsulfonate and even more effectively thanperfluorooctylsulfonate.

[0011] Another embodiment of the present invention relates to acomposition for treatment of fibrous substrates comprising a solution ofthe chemical composition of the present invention and a solvent. In thisembodiment, it is important that the chemical composition be dissolvedin the solvent. When applied to a substrate, this treatment compositionprovides a uniform distribution of the chemical composition on thesubstrate without altering the appearance of the substrate. With someembodiments a high temperature cure is not required to provide thiscoating; the treatment composition can be cured (i.e. dried) at ambienttemperatures. In other embodiments a high temperature cure (e.g.temperatures in above about 125° F. or 49° C.) may be used with coatingcompositions of the invention.

[0012] This invention also relates to an article comprising a fibroussubstrate having a cured coating derived from at least one solvent and achemical composition of the present invention. After application andcuring of the chemical composition, the substrate displays durablerelease/resistance/repellency properties.

[0013] This invention further relates to a method for impartingstain-release characteristics to a fibrous substrate, having one or moresurfaces, comprising the steps of:

[0014] (a) applying the coating composition of the present inventiononto one or more surfaces of the substrate and

[0015] (b) allowing the coating composition to cure (i.e. dry).

DEFINITIONS

[0016] Unless otherwise stated, the following terms used in thespecification and claims have the meanings given below:

[0017] “Acyloxy” means a radical —OC(O)R where R is, alkyl, alkenyl, andcycloalkyl, e.g., acetoxy, 3,3,3-trifluoroacetoxy, propionyloxy, and thelike.

[0018] “Alkoxy” means a radical —OR where R is an alkyl group as definedbelow, e.g., methoxy, ethoxy, propoxy, butoxy, and the like.

[0019] “Alkyl” means a linear saturated monovalent hydrocarbon radicalhaving from one to about twelve carbon atoms or a branched saturatedmonovalent hydrocarbon radical having from three to about twelve carbonatoms, e.g., methyl, ethyl, 1-propyl, 2-propyl, pentyl, and the like.

[0020] “Alkylene” means a linear saturated divalent hydrocarbon radicalhaving from one to about twelve carbon atoms or a branched saturateddivalent hydrocarbon radical having from three to about twelve carbonatoms, e.g., methylene, ethylene, propylene, 2-methylpropylene,pentylene, hexylene, and the like.

[0021] “Aryl aliphatic” means an alkylene radical defined above with anaromatic group attached to the alkylene radical, e.g., benzyl,pyridylmethyl, 1-naphthylethyl, and the like.

[0022] “Cured chemical composition” means that the chemical compositionis dried or solvent has evaporated from the chemical composition atambient temperature (15-35° C.) for up to approximately 24 hours or atelevated temperature until dryness.

[0023] “Fibrous substrate” means materials comprised of synthetic fiberssuch as wovens, knits, nonwovens, carpets, and other textiles; andmaterials comprised of natural fibers such as cotton, paper, andleather.

[0024] “Fluorocarbon monofunctional compound” means a compound havingone isocyanate-reactive functional group and a perfluoroalkyl or aperfluoroheteralkyl group, e.g. C₄F₉SO₂N(CH₃)CH₂CH₂OH,C₄F₉SO₂N(CH₃)CH₂CH₂NH₂, C₄F₉CH₂CH₂OH, C₄F₉CH₂CH₂SH,C₂F₅O(C₂F₄O)₃CF₂CONHC₂H₄OH, C₂F₅O(C₂F₄O)₃CF₂CONHC₂H₄CO₂H, C₆F₁₃CH₂OH,C6F13CH2N(CH₃)OH, and the like.

[0025] “Heteroacyloxy” has essentially the meaning given above foracyloxy except that one or more heteroatoms (i.e. oxygen, sulfur, and/ornitrogen) may be present in the R group and the total number of carbonatoms present may be up to 50, e.g., CH₃CH₂OCH₂CH₂C(O)O—,C₄H₉OCH₂CH₂OCH₂CH₂C(O)O—, CH₃O(CH₂CH₂O)_(n)CH₂CH₂C(O)O—, and the like.

[0026] “Heteroalkoxy” has essentially the meaning given above for alkoxyexcept that one or more heteroatoms (i.e. oxygen, sulfur, and/ornitrogen) may be present in the alkyl chain and the total number ofcarbon atoms present may be up to 50, e.g. CH₃CH₂OCH₂CH₂O—,C₄H₉OCH₂CH₂OCH₂CH₂O—, CH₃O(CH₂CH₂O)_(n)H, and the like.

[0027] “Heteroalkyl” has essentially the meaning given above for alkylexcept that one or more catenary heteroatoms (i.e. oxygen, sulfur,and/or nitrogen) may be present in the alkyl chain, these heteroatomsbeing separated from each other by at least one carbon, e.g.,CH₃CH₂OCH₂CH₂—, CH₃CH₂OCH₂CH₂OCH(CH₃)CH₂—, C₄F₉CH₂CH₂SCH₂CH₂—, and thelike.

[0028] “Heteroalkylene” has essentially the meaning given above foralkylene except that one or more catenary heteroatoms (i.e. oxygen,sulfur, and/or nitrogen) may be present in the alkylene chain, theseheteroatoms being separated from each other by at least one carbon,e.g., —CH₂OCH₂O—, —CH₂CH₂OCH₂CH₂—, —CH₂CH₂N(CH₃) CH₂CH₂—,—CH₂CH₂SCH₂CH₂—, and the like.

[0029] “Heteroaralkylene” means an aralkylene radical defined aboveexcept that catenary oxygen, sulfur, and/or nitrogen atoms may bepresent, e.g., phenyleneoxymethyl, phenyleneoxyethyl,benzyleneoxymethyl, and the like.

[0030] “Halo” means fluoro, chioro, bromo, or iodo, preferably fluoroand chloro.

[0031] “Isocyanate-reactive functional group” means a functional groupthat is capable of reacting with an isocyanate group, such as hydroxyl,amino, thiol, etc.

[0032] “Perfluoroalkyl” has essentially the meaning given above for“alkyl” except that all or essentially all of the hydrogen atoms of thealkyl radical are replaced by fluorine atoms and the number of carbonatoms is from 2 to about 12, e.g. perfluoropropyl, perfluorobutyl,perfluorooctyl, and the like.

[0033] “Perfluoroalkylene” has essentially the meaning given above for“alkylene” except that all or essentially all of the hydrogen atoms ofthe alkylene radical are replaced by fluorine atoms, e.g.,perfluoropropylene, periluorobutylene, perfluorooctylene, and the like

[0034] “Perfluoroheteroalkyl” has essentially the meaning given abovefor “heteroalkyl” except that all or essentially all of the hydrogenatoms of the heteroalkyl radical are replaced by fluorine atoms and thenumber of carbon atoms is from 3 to about 100, e.g. CF₃CF₂OCF₂CF₂—,CF₃CF₂O(CF₂CF₂O)₃CF₂CF₂—, C₃F₇O(CF(CF₃)CF₂O)_(m)CF(CF₃)CF₂—where m isfrom about 10 to about 30, and the like.

[0035] “Perfluoroheteroalkylene” has essentially the meaning given abovefor “heteroalkylene” except that all or essentially all of the hydrogenatoms of the heteroalkylene radical are replaced by fluorine atoms, andthe number of carbon atoms is from 3 to about 100, e.g., —CF₂OCF₂—,—CF₂O(CF₂O)_(n)(CF₂CF₂O)_(m)CF₂—, and the like.

[0036] “Perfluorinated group” means an organic group wherein all oressentially all of the carbon bonded hydrogen atoms are replaced withfluorine atoms, e.g. perfluoroalkyl, perfluoroheteroalkyl, and the like.

[0037] “Polyisocyanate compound” means a compound containing two or moreisocyanate radicals, —NCO, attached to a multivalent organic group, e.g.hexamethylene diisocyanate, the biuret and iscyanurate of hexamethylenediisocyanate, and the like.

[0038] “Reactive polyoxyalkylene” means a polymer having oxyalkylenerepeat units with an average of 1 or more isocyanate-reactive functionalgroups per molecule.

[0039] “Silane group” means a group comprising silicon to which at leastone hydrolyzable group is bonded, e.g. —Si(OCH₃)₃, —Si(OOCCH₃)₂CH₃,—Si(Cl)₃, and the like.

[0040] “Repellency” is a measure of a treated substrate's resistance towetting by oil and/or water and or adhesion of particulate soil.Repellency may be measured by the test methods described herein.

[0041] “Resistance” is the context or soiling or staining is a measureof the treated substrate's ability to avoid staining and/or soiling whencontacted by stain or soil respectively.

[0042] “Release” is a measure of the treated substrate's ability to havesoil and/or stain removed by cleaning or laundering.

[0043] “Release/resistance/repellency” means the compositiondemonstrates at least one of oil repellency, water repellency, stainrelease, stain repellency, soil release and soil repellency.

DETAILED DESCRIPTION OF THE INVENTION

[0044] The chemical compositions of the present invention comprise oneor more fluorochemical urethane compounds and one or more auxiliaryagents capable of further improving the resistance/release/repellency ofa fibrous substrate treated with the fluorochemical urethane compounds.This fluorochemical urethane compound(s) comprises the reaction productof (a) one or more polyfunctional isocyanate compounds; (b) one or morehydrophilic polyoxyalkylene compounds; (c) one or more fluorochemicalmonofunctional compounds; and (d) one or more silane compounds.

[0045] Each fluorochemical urethane compound comprises a urethane groupthat is derived or derivable from the reaction of at least onepolyfunctional isocyanate compound and at least one hydrophilicpolyoxyalkylene compound. The fluorochemical urethane compound isterminated, on average, with (i) one or more perfluoroalkyl groups, oneor more perfluoroheteroalkyl groups; and (ii) one or more silyl groups.It will be understood that the reaction product will provide a mixtureof compounds, some percentage of which will comprise compounds asdescribed, but may further comprise urethane compounds having differentsubstitution patterns and degree of substitution.

[0046] In one preferred embodiment, the composition of the presentinvention comprises 1) a mixture of urethane molecules arising from thereaction of (a) one or more polyfunctional isocyanate compounds, (b) oneor more hydrophilic polyoxyalkylene compounds, (c) one or morefluorochemical monofunctional compounds, and (d) one or more silanecompounds and 2) one or more auxiliary compounds as described above.

[0047] Generally, the amount of said hydrophilic polyoxyalkylenecompound is sufficient to react with between 0.1 and 30% of availableisocyanate groups, the amount of said silanes is sufficient to reactwith between 0.1 and 25% of available isocyanate groups, and the amountof said fluorochemical monofunctional compounds is sufficient to reactwith between 60 and 90% of available isocyanate groups. Preferably, theamount of said hydrophilic polyoxyalkylene(s) is sufficient to reactwith between 5 and 30% of available isocyanate groups, the amount ofsaid silanes is sufficient to react with between 0.1 and 15% ofavailable isocyanate groups, and the amount of said fluorochemicalmonofunctional compounds is sufficient to react with between 60 and 90%of available isocyanate groups.

[0048] Preferred classes of urethane compounds that may be present arerepresented by the following formulas:

[0049]R_(f)ZR²—X′(—CONH—Q(A)_(m)—NHCO—X′R³X′—)_(n)CONH—Q(A)—NHCO—X′R¹Si(Y)₃

[0050] R_(f)ZR²—X′(—CONH—Q(A)_(m)—NHCO—X′R³X′—)_(n)CONHR¹Si(Y)₃

[0051] wherein:

[0052] R_(f)ZR²— is a residue of at least one of the fluorochemicalmonofunctional compounds;

[0053] R_(f) is a perfluoroalkyl group having 2 to about 12 carbonatoms, or a perfluoroheteroalkyl group having 3 to about 50 carbonatoms;

[0054] Z is a covalent bond, sulfonamido (—SO₂NR—), or carboxamido(—CONR—) where R is hydrogen or alkyl;

[0055] R¹ is an alkylene, heteroalkylene, aralkylene, orheteroaralkylene group;

[0056] R² is a divalent straight or branched chain alkylene,cycloalkylene, or heteroalkylene group of 1 to 14 carbon atoms,preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, andmost preferably two carbon atoms, and preferably R² is alkylene orheteroalkylene of 1 to 14 carbon atoms;

[0057] Q is a multi-valent organic group that is a residue of thepolyfunctional isocyanate compound;

[0058] R³ is a polyvalent, preferably divalent organic group which is aresidue of the hydrophilic polyoxyalkylene;

[0059] X′ is —O—, —S—, or —N(R)—, wherein R is hydrogen or C₁-C₄ alkyl;

[0060] each Y is independently a hydroxy; a hydrolyzable moiety selectedfrom the group consisting of alkoxy, acyloxy, heteroalkoxy,heteroacyloxy, halo, and oxime; or a non-hydrolyzable moiety selectedfrom the group consisting of phenyl, alicyclic, straight-chainaliphatic, and branched-chain aliphatic, wherein at least one Y is ahydrolyzable moiety.

[0061] A is selected from the group consisting of R_(f)ZR²—OCONH—,(Y)₃SiR¹XCONH—, and (Y)₃SiR¹NHCOOR³OCONH—.

[0062] m is an integer from 0 to 2; and

[0063] n is an integer from 1 to 10.

[0064] It will be understood with respect to the above formulas that thecompounds represent theoretical structures for the reaction products.The reaction product will contain a mixture of compounds in which thesubstitution patterns of the isocyanate groups will vary.

[0065] Polyfunctional isocyanate compounds useful in the presentinvention comprise isocyanate groups attached to the multivalent organicgroup, Q, which can comprise a multivalent aliphatic, alicyclic, oraromatic moiety; or a multivalent aliphatic, alicyclic or aromaticmoiety attached to a blocked isocyanate, a biuret, an isocyanurate, or auretdione, or mixtures thereof. Preferred polyfunctional isocyanatecompounds contain at least two and preferably three or more —NCO groups.Compounds containing two —NCO groups are comprised of divalentaliphatic, alicyclic, araliphatic, or aromatic moieties to which the—NCO radicals are attached. Preferred compounds containing three —NCOradicals are comprised of isocyanatoaliphatic, isocyanatoalicyclic, orisocyanatoaromatic, monovalent moieties, which are attached to a biuretor an isocyanurate.

[0066] Representative examples of suitable polyfunctional isocyanatecompounds include isocyanate functional derivatives of thepolyfunctional isocyanate compounds as defined herein. Examples ofderivatives include, but are not limited to, those selected from thegroup consisting of ureas, biurets, allophanates, dimers and trimers(such as uretdiones and isocyanurates) of isocyanate compounds, andmixtures thereof. Any suitable organic polyisocyanate, such as analiphatic, alicyclic, araliphatic, or aromatic polyisocyanate, may beused either singly or in mixtures of two or more.

[0067] The aliphatic polyfunctional isocyanate compounds generallyprovide better light stability than the aromatic compounds, and arepreferred for treatment of fibrous substrates. Aromatic polyfunctionalisocyanate compounds, on the other hand, are generally more economicaland reactive toward hydrophilic polyoxyalkylene compounds and otherisocyanate-reactive compounds than are aliphatic polyfunctionalisocyanate compounds.

[0068] Suitable aromatic polyfunctional isocyanate compounds include,but are not limited to, those selected from the group consisting of2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate, an adduct ofTDI with trimethylolpropane (available as Desmodur™ CB from BayerCorporation, Pittsburgh, Pa.), the isocyanurate trimer of TDI (availableas Desmodur™ IL from Bayer Corporation, Pittsburgh, Pa.),diphenylmethane 4,4′-diisocyanate (MDI), diphenylmethane2,4′-diisocyanate, 1,5-diisocyanato-naphthalene, 1,4-phenylenediisocyanate, 1,3-phenylene diisocyanate, 1-methyoxy-2,4-phenylenediisocyanate, 1-chlorophenyl-2,4-diisocyanate, and mixtures thereof.

[0069] Examples of useful alicyclic polyfunctional isocyanate compoundsinclude, but are not limited to, those selected from the groupconsisting of dicyclohexylmethane diisocyanate (H₁₂MDI, commerciallyavailable as Desmodur™W, available from Bayer Corporation, Pittsburgh,Pa.), 4,4′-isopropyl-bis(cyclohexylisocyanate), isophorone diisocyanate(IPDI), cyclobutane-1,3-diisocyanate, cyclohexane 1,3-diisocyanate,cyclohexane 1,4-diisocyanate (CHDI), 1,4-cyclohexanebis(methyleneisocyanate) (BDI), 1,3-bis(isocyanatomethyl)cyclohexane (H₆XDI),3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, and mixturesthereof.

[0070] Examples of useful aliphatic polyfunctional isocyanate compoundsinclude, but are not limited to, those selected from the groupconsisting of 1,4-tetramethylene diisocyanate, hexamethylene1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), 1,12-dodecanediisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate (TMDI),2,4,4-trimethyl-hexamethylene diisocyanate (TMDI),2-methyl-1,5-pentamethylene diisocyanate, dimer diisocyanate, the ureaof hexamethylene diisocyanate, the biuret of hexamethylene1,6-diisocyanate (HDI) (available as Desmodur™ N-100 and N-3200 fromBayer Corporation, Pittsburgh, Pa.), the isocyanurate of HDI (availableas Demodur™ N-3300 and Desmodurm™ N-3600 from Bayer Corporation,Pittsburgh, Pa.), a blend of the isocyanurate of HDI and the uretdioneof HDI (available as Desmodur™ N-3400 available from Bayer Corporation,Pittsburgh, Pa.), and mixtures thereof.

[0071] Examples of useful aryl aliphatic polyisocyanates include, butare not limited to, those selected from the group consisting ofm-tetramethyl xylylene diisocyanate (m-TMXDI), p-tetramethyl xylylenediisocyanate (p-TMXDI), 1,4-xylylene diisocyanate (XDI), 1,3-xylylenediisocyanate, p-(1-isocyanatoethyl)-phenyl isocyanate,m-(3-isocyanatobutyl)-phenyl isocyanate,4-(2-isocyanatocyclohexyl-methyl)-phenyl isocyanate, and mixturesthereof.

[0072] Preferred polyisocyanates, in general, include those selectedfrom the group consisting of hexamethylene 1,6-diisocyanate (HDI),1,12-dodecane diisocyanate isophorone diisocyanate, toluenediisocyanate, dicyclohexylmethane 4,4′-diisocyanate, MDI, derivatives ofall the aforementioned, including Desmodur™ N-100, N-3200, N-3300,N-3400, N-3600, and mixtures thereof.

[0073] Suitable commercially available polyfunctional isocyanates areexemplified by Desmodur™ N-3200, Desmodur™ N-3300, Desmodur™ N-3400,Desmodur™ N-3600, Desmodur™ H (HDI), Desmodur™ W(bis[4-isocyanatocyclohexyl]methane), Mondur™ M(4,4′-diisocyanatodiphenylmethane), Mondur™ TDS (98% toluene2,4-diisocyanate), Mondur™ TD-80 (a mixture of 80% 2,4 and 20%2,6-toluene diisocyanate isomers), and Desmodur™ N-100, each availablefrom Bayer Corporation, Pittsburgh, Pa.

[0074] Other useful triisocyanates are those obtained by reacting threemoles of a diisocyanate with one mole of a triol. For example, toluenediisocyanate, 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate,or m-tetramethylxylene diisocyanate can be reacted with1,1,1-tris(hydroxymethyl)propane to form triisocyanates. The productfrom the reaction with m-tetramethylxylene diisocyanate is commerciallyavailable as CYTHANE 3160 (American Cyanamid, Stamford, Conn.).

[0075] Hydrophilic polyoxyalkylene compounds suitable for use inpreparing the first component fluorochemical urethane compounds of thepresent invention include those polyoxyalkylene compounds that have anaverage functionality of greater than 1 (preferably, about 2 to 5; morepreferably, about 2 to 3; most preferably, about 2, as difunctionalcompounds such as diols are most preferred). The isocyanate-reactivegroups can be primary or secondary, with primary groups being preferredfor their greater reactivity. Mixtures of compounds having differentfunctionalities, for examples mixtures of polyoxyalkylene compoundshaving one, two and three isocyanate-reactive groups, may be usedprovide the average is greater than 1. The polyoxyalkylene groupsinclude those having 1 to 3 carbon atoms such as polyoxyethylene,polyoxypropylene, and copolymers thereof such as polymers having bothoxyethylene and oxypropylene units.

[0076] Examples of polyoxyalkylene containing compounds include alkylethers of polyglycols such as e.g. methyl or ethyl ether of polyethyleneglycol, hydroxy terminated methyl or ethyl ether of a random or blockcopolymer of ethylene oxide and propylene oxide, amino terminated methylor ethyl ether of polyethyleneoxide, polyethylene glycol, polypropyleneglycol, a hydroxy terminated copolymer (including a block copolymer) ofethylene oxide and propylene oxide, a mono- or diamino-terminatedpoly(alkylene oxide) such as Jeffamine™ ED, Jeffamine™ EDR-148 andpoly(oxyalkylene) thiols. Commercially available aliphaticpolyisocyanates include Baygard™ VP SP 23012, Rucoguard™ EPF 1421 andTubicoat™ Fix ICB.

[0077] Useful commercially available hydrophilic polyoxyalkylenecompounds for the first component include Carbowax™ poly(ethyleneglycol) materials in the number average molecular weight (M_(n)) rangeof from about 200 to about 2000 (available from Union Carbide Corp.);poly(propylene glycol) materials such as PPG-425 (available fromLyondell Chemicals); block copolymers of poly(ethylene glycol) andpoly(propylene glycol) such as Pluronic™ L31 (available from BASFCorporation); the “PeP” series (available from Wyandotte ChemicalsCorporation) of polyoxyalkylene tetrols having secondary hydroxylgroups, for example, “PeP” 450, 550, and 650.

[0078] Fluorochemical monofunctional compounds suitable for use inpreparing the chemical compositions of the present invention includethose that comprise at least one R_(f) group. The R_(f) groups cancontain straight chain, branched chain, or cyclic fluorinated alkylenegroups or any combination thereof. The R_(f) groups can optionallycontain one or more heteroatoms (i.e. oxygen, sulfur, and/or nitrogen)in the carbon-carbon chain so as to form a carbon-heteroatom-carbonchain (i.e. a heteroalkylene group). Fully-fluorinated groups aregenerally preferred, but hydrogen or chlorine atoms can also be presentas substituents, provided that no more than one atom of either ispresent for every two carbon atoms. It is additionally preferred thatany R_(f) group contain at least about 40% fluorine by weight, morepreferably at least about 50% fluorine by weight. The terminal portionof the group is generally fully-fluorinated, preferably containing atleast three fluorine atoms, e.g., CF₃O—, CF₃CF₂—, CF₃CF₂CF₂—, (CF₃)₂N—,(CF₃)₂CF—, SF₅CF₂—. Perfluorinated aliphatic groups (i.e., those of theformula C_(n)F_(2n+1)—) wherein n is 2 to 12 inclusive are the preferredR_(f) groups, with n=3 to 5 being more preferred and with n=4 being themost preferred.

[0079] Useful fluorochemical monofunctional compounds include compoundsof the following formula:

R_(f)—Z—R²—X

[0080] wherein:

[0081] R_(f) is a perfluoroalkyl group or a perfluoroheteroalkyl groupas defined above;

[0082] Z is a connecting group selected from a covalent bond, asulfonamido group, a carboxamido group, a carboxyl group, or a sulfonylgroup; and

[0083] R² is a divalent straight or branched chain alkylene,cycloalkylene, or

[0084] heteroalkylene group of 1 to 14 carbon atoms, preferably 1 to 8carbon atoms,

[0085] more preferably 1 to 4 carbon atoms, and most preferably twocarbon atoms, and

[0086] X is an isocyanate-reactive functional groups, for example —NH₂;—SH; —OH; —N═C═O; or —NRH where R is H or a C₁C₄ alkyl.

[0087] Representative examples of useful fluorochemical monofunctionalcompounds include the following: CF₃(CF₂)₃SO₂N(CH₃)CH₂CH₂OH,CF₃(CF₂)₃SO₂N(CH₃)CH(CH₃)CH₂OH, CF₃(CF₂)₃SO₂N(CH₃)CH₂CH(CH₃)NH₂,CF₃(CF₂)₃SO₂N(CH₂CH₃)CH₂CH₂SH, CF₃(CF₂)₃SO₂N(CH₃)CH₂CH₂SCH₂CH₂OH,C₆F₁₃SO₂N(CH₃)(CH₂)₄OH, CF₃(CF₂)₇SO₂N(H)(CH₂)₃OH, C₃F₇SO₂N(CH₃)CH₂CH₂OH,CF₃(CF₂)₄SO₂N(CH₃)(CH₂)₄NH₂, C₄F₉SO₂N(CH₃)(CH₂)₁₁OH,CF₃(CF₂)₅SO₂N(CH₂CH₃)CH₂CH₂OH, CF₃(CF₂)₅SO₂N(C₂H₅)(CH₂)₆OH,CF₃(CF₂)₂SO₂N(C₂H₅)(CH₂)₄OH, CF₃(CF₂)₃SO₂N(C₃H₇)CH₂OCH₂CH₂CH₂ OH,CF₃(CF₂)₄SO₂N(CH₂CH₂CH₃)CH₂CH₂OH, CF₃(CF₂)₄SO₂N(CH₂CH₂CH₃)CH₂CH₂N HCH₃,CF₃(CF₂)₃SO₂N(C₄H₉)CH₂CH₂NH₂, CF₃(CF₂)₃SO₂N(C₄H₉)(CH₂)₄SH,CF₃(CF₂)₃CH₂CH₂OH C₄F₉OC₂F₄OCF₂CH₂OCH₂CH₂OH;n-C₆F₁₃CF(CF₃)CON(H)CH₂CH₂OH; C₆F₁₃CF(CF₃)CO₂C₂H₄CH(CH₃)OH;C₃F₇CON(H)CH₂CH₂OH; C₃F₇O(CF(CF₃)CF₂O)₁₋ ₃₆CF(CF₃)CH₂OH;

[0088] and the like, and mixtures thereof. If desired, otherisocyanate-reactive functional groups may be used in place of thosedepicted.

[0089] Silane compounds suitable for use in the chemical compositions ofthe present invention are those of the following formula:

X—R¹—Si—(Y)₃

[0090] wherein X, R¹, and Y are as defined previously. Therefore, thesesilane compounds contain one, two, or three hydrolysable groups (Y) onthe silicon and one organic group including an isocyanate-reactive or anactive hydrogen reactive radical (X—R¹). Any of the conventionalhydrolysable groups, such as those selected from the group consisting ofalkoxy, acyloxy, heteroalkoxy, heteroacyloxy, halo, oxime, and the like,can be used as the hydrolyzable group (Y). The hydrolysable group (Y) ispreferably alkoxy or acyloxy and more preferably alkoxy.

[0091] When Y is halo, the hydrogen halide liberated from thehalogen-containing silane can cause polymer degradation when cellulosesubstrates are used. When Y is an oxime group, lower oxime groups of theformula —N═CR⁵R⁶, wherein R⁵ and R⁶ are monovalent lower alkyl groupscomprising about 1 to about 12 carbon atoms, which can be the same ordifferent, preferably selected from the group consisting of methyl,ethyl, propyl, and butyl, are preferred.

[0092] Representative divalent bridging radicals (R₁) include, but arenot limited to, those selected from the group consisting of —CH₂CH₂—,—CH₂CH₂CH₂—, —CH₂CH₂CH₂OCH₂CH₂—, —CH₂CH₂C₆H₄CH₂CH₂—, and—CH₂CH₂O(C₂H₄O)₂CH₂CH₂N(CH₃)CH₂CH₂CH₂—.

[0093] Other preferred silane compounds are those which contain one ortwo hydrolyzable groups, such as those having the structuresR²OSi(R⁷)₂R¹XH and (R⁸O)₂Si(R⁷)R¹XH, wherein R¹ is as previouslydefined, and R⁷ and R⁸ are selected from the group consisting of aphenyl group, an alicycylic group, or a straight or branched aliphaticgroup having from about 1 to about 12 carbon atoms. Preferably, R⁷ andR⁸ are a lower alkyl group comprising 1 to 4 carbon atoms.

[0094] Following the hydrolysis of some of these terminal silyl groups,inter-reaction with a substrate surface comprising —SiOH groups or othermetal hydroxide groups to form siloxane or metal-oxane linkages, e.g.,

[0095] can occur. Bonds thus formed, particularly Si—O—Si bonds, arewater resistant and can provide enhanced durability of the stain-releaseproperties imparted by the chemical compositions of the presentinvention.

[0096] Such silane compounds are well known in the art and many arecommercially available or are readily prepared. Representativeisocyanate-reactive silane compounds include, but are not limited to,those selected from the group consisting of: H₂NCH₂CH₂CH₂Si(OC₂H₅)₃;H₂NCH₂CH₂CH₂Si(OCH₃)₃; H₂NCH₂CH₂CH₂Si(O—N═C(CH₃)(C₂H₅))₃HSCH₂CH₂CH₂Si(OCH₃)₃; HO(C₂H₄O)₃C₂H₄N(CH₃)(CH₂)₃Si(OC₄H₉)₃;H₂NCH₂C₆H₄CH₂CH₂Si(OCH₃)₃; HSCH₂CH₂CH₂Si(OCOCH₃)₃;HN(CH₃)CH₂CH₂Si(OCH₃)₃; HSCH₂CH₂CH₂SiCH₃(OCH₃)₂;(H3CO)₃SiCH₂CH₂CH₂NHCH₂CH₂CH₂ Si(OCH₃)₃; HN(CH₃)C₃H₆Si(OCH₃)₃;CH₃CH₂OOCCH₂CH(COOCH₂CH₃)HNC₃ H₆Si(OCH₂CH₃)₃; C₆H₅NHC₃H₆Si(OCH₃)₃;H₂NC₃H₆SiCH₃(OCH₂CH₃)₂; HOCH(CH₃)CH₂OCONHC₃H₆Si(OCH₂CH₃)₃;(HOCH₂CH₂)₂NCH₂CH₂CH₂Si(OCH₂CH₃)₃ H₂NCH₂CH₂NHCH₂CH₂CH₂Si(OC₂H₅)₃H₂NCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃

[0097] and mixtures thereof.

[0098] The chemical compositions of the present invention may be madeaccording to the following step-wise synthesis. As one skilled in theart would understand, the order of the steps is non-limiting and can bemodified so as to produce a desired chemical composition. In thesynthesis, the polyfunctional isocyanate compound and the monofunctionalfluorochemical compound are dissolved together under dry conditions,preferably in a solvent, and then heating the resulting solution atapproximately 40 to 80° C., preferably approximately 60 to 70° C., withmixing in the presence of a catalyst for one-half to two hours,preferably one hour. Depending on reaction conditions (e.g., reactiontemperature and/or polyfunctional isocyanate used), a catalyst level ofup to about 0.5 percent by weight of the polyfunctionalisocyanate/polyoxyalkylene mixture may be used, but typically about0.00005 to about 0.5 percent by weight is required, 0.02 to 0.1 percentby weight being preferred.

[0099] Suitable catalysts include, but are not limited to, tertiaryamine and tin compounds. Examples of useful tin compounds include tin IIand tin IV salts such as stannous octanoate, dibutyltin dilaurate,dibutyltin diacetate, dibutyltin di-2-ethylhexanoate, anddibutyltinoxide. Examples of useful tertiary amine compounds includetriethylamine, tributylamine, triethylenediamine, tripropylamine,bis(dimethylaminoethyl) ether, morpholine compounds such as ethylmorpholine, and 2,2′-dimorpholinodiethyl ether,1,4-diazabicyclo[2.2.2]octane (DABCO, Aldrich Chemical Co., Milwaukee,Wis.), and 1,8-diazabicyclo[5.4.0.]undec-7-ene (DBU, Aldrich ChemicalCo., Milwaukee, Wis.). Tin compounds are preferred.

[0100] The resulting fluorochemical functional urethane compounds andcompounds are then further reacted with one or more of the silanecompounds described above. The silane compound is added to the abovereaction mixture, and reacts with a substantial portion of the remainingNCO groups. The above temperatures, dry conditions, and mixing arecontinued one-half to two hours, preferably one hour. Terminalsilane-containing groups are thereby bonded to the isocyanate functionalurethane compounds. Aminosilanes are preferred, because of the rapid andcomplete reaction that occurs between the remaining NCO groups and thesilane compound's amino groups. Isocyanato functional silane compoundsmay be used and are preferred when the ratio of polyfunctionalisocyanate compound to the hydrophilic difunctional polyoxyalkylene andfluorochemical monofunctional compound is such that the resultingcompound has a terminal hydroxyl group.

[0101] These compounds are further functionalized with polyoxyalkylenecompounds, having an average functionality of greater than 1, describedabove by reacting any of the remaining NCO groups in the resultingmixture with one or more of the reactive polyoxyalkylene compoundsdescribed above. Thus, the polyoxyalkylene compound(s) is (are) added tothe reaction mixture, using the same conditions as with the previousadditions.

[0102] The coating composition of the invention further comprises asecond auxiliary compound that is capable of improving the durability ofthe repellency/resistant/release properties. In particular, the secondcomponent improves the stain release in general and the durability ofthe soil release. The auxiliary compounds are generally non-fluorinatedorganic compounds and are also called extenders hereinafter. Suitableextenders capable of improving the oil- and/or water repellencyproperties include for example blocked isocyanates including aromaticand aliphatic blocked isocyanates, aliphatic polyisocyanates andaromatic or aliphatic carbodiimides including aromatic or aliphaticpolycarbodiimides. Auxiliary compounds that are capable of enhancing thesoil/stain release properties are generally non-fluorinated organiccompounds such as for example blocked isocyanate compounds that includea polyoxyalkylene group, in particular a polyoxyethylene group.Auxiliary compounds that are generally capable of improving durabilityof the repellency properties or soil/stain release properties includenon-fluorinated organic compounds that have one or more groups (or aprecursor thereof) capable of reacting with the surface of the fibroussubstrate. Examples thereof include compounds that have isocyanategroups or blocked isocyanates as described herein.

[0103] Polyisocyanates useful in preparing the second component extenderinclude those previously described for the first component. Inparticularly, the previously described aliphatic isocyanates arepreferred due to their better light stability.

[0104] The aliphatic polyisocyanate for use in the second component asan extender in the fluorochemical composition is preferably a compoundhaving a molecular weight of at least 350 g/mole. The amount of freeisocyanate groups in the aliphatic isocyanate is typically at least 10%by weight of the total weight of the compound, preferably at least 20%by weight. Suitable low molecular weight aliphatic isocyanates includediisocyanates, triisocyanates and mixtures thereof. Examples includehexamethylenediisocyanate,2,2,4-trimethyl-1,6-hexamethylenediisocyanate, and1,2-ethylenediisocyanate, dicyclohexylmethane-4,4′-diisocyanate,aliphatic triisocyanates such as 1,3,6-hexamethylenetriisocyanate,cyclic trimer of hexamethylenediisocyanate and cyclic trimer ofisophorone diisocyanate (isocyanurates).

[0105] The polyoxyalkylene compound is generally reacted with thealiphatic polyisocyanate in the presence of a catalyst such as anorganic tin compound and under reaction conditions commonly employed.Polyoxyalkylene compounds useful in preparing the second componentextender include those previously described for the first component.However, the polyoxyalkylene component preferably has a functionality ofless than two and is more preferably one. Mixtures of polyoxyalkylenecompounds having different degrees of functionality may be used,provided that the average functionality is less than two. Usefulfunctional groups include any group that is reactive toward theisocyanate groups of the second component polyisocyanate, for example—NH₂; —SH; —OH; —N═C═O; or —NRH, where R is a lower alkyl.Monofunctional polyoxyalkylene compounds are preferred.

[0106] The amount of polyoxyalkylene compound will be selected such asto leave a desired amount of isocyanate groups unreacted. Generally theamount of polyoxyalkylene compound is such that from about 25 to about75%, preferably 25 to 40% of the available isocyanate groups arereacted. The remaining isocyanate groups may be free isocyanate groupsor may be preferably blocked isocyanate groups. The resultant reactionmixture can be used in compositions of the invention.

[0107] The polyoxyalkylene groups include those having 1 to 3 carbonatoms such as polyoxyethylene, polyoxypropylene, polyoxytetramethyleneand copolymers thereof such as polymers having both oxyethylene andoxypropylene units. The polyoxyalkylene containing organic compound mayinclude one or two functional groups such as hydroxy or amino groups.Examples of polyoxyalkylene containing compounds include alkyl ethers ofpolyglycols such as e.g. methyl or ethyl ether of polyethyleneglycol,hydroxy terminated methyl or ethyl ether of a random or block copolymerof ethyleneoxide and propyleneoxide, amino terminated methyl or ethylether of polyethyleneoxide, polyethylene glycol, polypropylene glycol, ahydroxy terminated copolymer (including a block copolymer) ofethyleneoxide and propylene oxide, a diamino terminated poly(alkyleneoxide) such as Jeffamine™ ED, Jeffamine™ EDR-148 and poly(oxyalkylene)thiols. Commercially available aliphatic polyisocyanates includeBaygard™ VP SP 23012, Rucoguard™ EPF 1421 and Tubicoat™ Fix ICB.

[0108] A “blocked isocyanate” is a polyisocyanate of a portion of theisocyanate groups have been reacted with a blocking agent. Isocyanateblocking agents are compounds that upon reaction with an isocyanategroup yield a group that is unreactive at room temperature withcompounds that at room temperature normally react with an isocyanate butwhich group at elevated temperature reacts with isocyanate reactivecompounds. Generally, at elevated temperature the blocking group will bereleased from the blocked polyisocyanate group thereby generating theisocyanate group again which can then react with an isocyanate reactivegroup, such as may be found on the surface of a fibrous substrate.Blocking agents and their mechanisms have been described in detail in“Blocked isocyanates III.: Part. A, Mechanisms and chemistry” by DouglasWicks and Zeno W. Wicks Jr., Progress in Organic Coatings, 36 (1999),pp. 14-172.

[0109] The blocked isocyanate may be aromatic, aliphatic, cyclic oracyclic and is generally a blocked di- or triisocyanate or a mixturethereof and can be obtained by reacting an isocyanate with a blockingagent that has at least one functional group capable of reacting with anisocyanate group. Preferred blocked isocyanates are blockedpolyisocyanates that, at a temperature of less than 150° C., are capableof reacting with an isocyanate reactive group, through deblocking of theblocking agent at elevated temperature. Preferred blocking agentsinclude arylalcohols such as phenols, lactams such as ε-caprolactam,δ-valerolactam, γ-butyrolactam, oximes such as formaldoxime,acetaldoxime, methyl ethyl ketone oxime, cyclohexanone oxime,acetophenone oxime, benzophenone oxime, 2-butanone oxime or diethylglyoxime. Further suitable blocking agents include bisulfite andtriazoles.

[0110] According to a particular embodiment of the invention, theblocked polyisocyanate may comprise the condensation product of apolyisocyanate, for example a di- or triisocyanate, a blocking agent,and an polyoxyalkylene compound, the polyoxyalkylene compound having oneor more, preferably one, isocyanate reactive groups such as a hydroxy,amino or thiol group. Examples of such organic compounds include thosedescribed above. Particularly preferred are blocked polyisocyanates thathave a self-emulsifying capability in water. The use of blockedisocyanate compounds are particularly useful in fibrous substrate whenco-applied with permanent press treatments, which require elevatedtemperatures during application.

[0111] Examples of polyisocyanates for preparing the blockedpolyisocyanates include di- or triisocyanates as well as mixturesthereof. Specific examples are aromatic diisocyanates such as4,4′-methylenediphenylenediisocyanate,4,6-di-(trifluoromethyl)-1,3-benzene diisocyanate,2,4-toluenediisocyanate, 2,6-toluene diisocyanate, o, m, and p-xylylenediisocyanate, 4,4′-diisocyanatodiphenylether,3,3′-dichloro-4,4′-diisocyanatodiphenylmethane,4,5′-diphenyldiisocyanate, 4,4′-diisocyanatodibenzyl,3,3′-dimethoxy-4,4′-diisocyanatodiphenyl,3,3′-dimethyl-4,4′-diisocyanatodiphenyl,2,2′-dichloro-5,5′-dimethoxy-4,4′-diisocyanato diphenyl,1,3-diisocyanatobenzene, 1,2-naphthylene diisocyanate,4-chloro-1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, and1,8-dinitro-2,7-naphthylene diisocyanate and aromatic tri-isocyanatessuch as polymethylenepolyphenylisocyanate.

[0112] Still further isocyanates that can be used for preparing ablocked isocyanate include alicyclic diisocyanates such as3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate;3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate; aliphaticdiisocyanates such as 1,6-hexamethylenediisocyanate,2,2,4-trimethyl-1,6-hexamethylenediisocyanate, and1,2-ethylenediisocyanate; aliphatic triisocyanates such as1,3,6-hexamethylenetriisocyanate; aromatic tri-isocyanates such aspolymethylenepolyphenylisocyanate (PAPI); cyclic diisocyanates such asisophorone diisocyanate (IPDI) anddicyclohexylmethane-4,4′-diisocyanate. Also useful are isocyanatescontaining internal isocyanate-derived moieties such asbiuret-containing tri-isocyanates such as that available from Bayer asDESMODUR™ N-100, isocyanurate-containing tri-isocyanates such as thatavailable from Huls AG, Germany, as IPDI-1890, andazetedinedione-containing diisocyanates such as that available fromBayer as DESMODUR™ TT. Also, other di- or tri-isocyanates such as thoseavailable from Bayer as DESMODUR™ L and DESMODUR™ W, andtri-(4-isocyanatophenyl)-methane (available from Bayer as DESMODUR™ R)are suitable.

[0113] Commercially available blocked aromatic polyisocyanates includeBaygard™ EDW available from Bayer Corp. and Hydrophobol™ XAN availablefrom Ciba-Geigy.

[0114] A still further class of extenders suitable for use with thefluorochemical composition of this invention are hydrophiliccarbodiimides. Suitable carbodiimides have been described in for exampleU.S. Pat. Nos. 4,668,726, 4,215,205, 4,024,178, 3,896,251, WO 93/22282,U.S. Pat. Nos. 5,132,028, 5,817,249, 4,977,219, 4,587,301, 4,487,964,3,755,242 and 3,450,562. Particularly suitable carbodiimides for use inthis invention include those corresponding to the formula:

R¹—[N═C═N—R³]_(u)—N═C═N—R²

[0115] wherein u has a value of 1 to 10, typically 1 or 2, R¹ and R²each independently represent a hydrocarbon group, in particular alinear, branched or cyclic aliphatic group preferably having 6 to 18carbon atoms and R³ represents a divalent linear, branched or cyclicaliphatic group.

[0116] Yet a further class of extenders that can be advantageously usedas the second component in a fluorochemical urethane treatmentcomposition of this invention include hydrophilic polymers of acrylicand/or methacrylic monomers. Particular examples of such polymersinclude homo- and copolymers of partial alkyl esters of acrylic andmethacrylic acid such as for example C₁ to C₃₀ alkyl esters of acrylicacid. Such acrylates should have sufficient free (unesterified) carboxylgroups to provide the requisite hydrophilicity. Specific examples ofsuch alkyl esters include methyl acrylate, ethyl acrylate, butylacrylate, octadecyl acrylate and lauryl acrylate. Specific examples ofsuitable polymers include a homopolymer of methyl acrylate and acopolymer of methyl acrylate and octadecyl acrylate. One particularlyuseful product is FC-672™, an acrylate stainblocker available from the3M Company

[0117] The ratio of the first component fluorochemical urethanecompound(s) to the second component auxiliary compound may be from about12:1 to 1:12 and is typically from about 3:1 to 6:1.

[0118] The treatment composition for fibrous substrates comprises asolution of the chemical compositions of the present invention and atleast one solvent. When applied to fibrous substrates, the treatmentcompositions impart stain-release characteristics and exhibit durability(i.e. they resist being worn-off) when exposed to wear and abrasion fromuse, cleaning, and the elements.

[0119] The chemical compositions of the present invention can bedissolved in a variety of solvents to form coating compositions suitablefor use in coating the chemical compositions of the present inventiononto a substrate. Fibrous substrate treatment compositions may containfrom about 0.1 to about 50 weight percent chemical composition.Preferably the chemical composition is used in the coating compositionat about 0.1 to about 10 weight percent, most preferably from about 2 toabout 4 weight percent.

[0120] Suitable solvents include water, alcohols, esters, glycol ethers,amides, ketones, hydrocarbons, chlorohydrocarbons, chlorocarbons, andmixtures thereof. Depending upon the substrate to which the compositionis being applied, water is the preferred solvent because it does notraise any environmental concerns and is accepted as safe and non-toxic.

[0121] The treatment compositions of the present invention can beapplied as to a wide variety of fibrous substrates resulting in anarticle that displays durable stain-release properties. The article ofthe present invention comprises a fibrous substrate having a treatmentderived from at least one solvent and a chemical composition of thepresent invention. After application and curing of the coatingcomposition, the substrate displays durable stain-release properties.

[0122] The treatment composition may also be applied to other substratesincluding glass, ceramic, stone, metal, semi-porous materials such asgrout, cement and concrete, wood, paint, plastics, rubber.

[0123] The treatment compositions of the present invention can beapplied to a wide variety of fibrous substrates including woven, knit,and nonwoven fabrics, textiles, carpets, leather, and paper. Substrateshaving nucleophilic groups, such as cotton are preferred because theycan bond to the silane groups and/or isocyanate groups of the chemicalcompositions of the present invention, thereby increasing durability ofthe fiber treatment. Any application method known to one skilled in theart can be used including spraying, dipping, immersion, foaming,atomizing, aerosolizing, misting, flood-coating, and the like.

[0124] To impart release/repellency/resistance characteristics to afibrous substrate, the coating composition of the present invention isapplied to the substrate and is allowed to cure (i.e. dry), at ambientor elevated temperature.

[0125] In order to affect treatment of the fibrous substrate the fibroussubstrate is contacted with the fluorochemical composition of theinvention. For example, the substrate can be immersed in thefluorochemical treating composition. The treated substrate can then berun through a padder/roller to remove excess fluorochemical compositionand dried or cured. The treated substrate may be dried at roomtemperature by leaving it in air or may alternatively or additionally besubjected to a heat treatment, for example, in an oven. A heat treatmentis typically carried out at temperatures between about 50° C. and about190° C. depending on the particular system or application method used.In general, a temperature of about 120° C. to 170° C., in particular ofabout 150° C. to about 170° C. for a period of about 20 seconds to 10minutes, preferably 3 to 5 minutes, is suitable. Alternatively, thechemical composition can be applied by spraying the composition on thefibrous substrate. An ambient cure preferably takes place atapproximately 15 to 35° C. (i.e. ambient temperature) until dryness isachieved, up to approximately 24 hours. With either heat-treatment orambient cure, the chemical composition can also form chemical bonds withthe substrate and between molecules of the chemical composition.

[0126] The choice of either heat-treatment or ambient cure often dependson the desired end-use. For consumer applications, where the compositionmay be applied to household laundry or carpeting, and ambient cure isdesired. For industrial applications, where the fibrous substrate, suchas a textile might normally be exposed to elevated temperatures duringproduction, an elevated temperature cure or heat-treatment may bedesirable. Generally, those composition containing blocked isocyanategroups are preferred where a heat-treatment is encountered

[0127] The amount of the treating composition applied to the fibroussubstrate is chosen so that a sufficiently high level of the desiredproperties are imparted to the substrate surface without substantiallyaffecting the look and feel of the treated substrate. Such amount isusually such that the resulting amount of the fluorochemical urethanecomposition on the treated fibrous substrate will be between 0.05% and5% by weight based on the weight of the fibrous substrate, known assolids on fiber or SOF. The amount that is sufficient to impart desiredproperties can be determined empirically and can be increased asnecessary or desired.

[0128] Fibrous substrates that can be treated with the fluorochemicalcomposition include in particular textiles. The fibrous substrate may bebased on synthetic fibers, e.g. polyester, polyamide and polyacrylatefibers or natural fibers, e.g. cellulose fibers as well as mixturesthereof. The fibrous substrate may be a woven as well as a non-wovensubstrate. Preferred substrates are cellulosic materials such as cotton,rayon, TENCEL™ and blends of cellulosic materials.

[0129] The resulting treated substrates derived from at least onesolvent and a chemical composition of the present invention, have beenfound to be resist soils and/or stains and/or to release soils and/orstains with simple washing methods. The cured treatments have also beenfound to be durable and hence to resist being worn-off due to wear andabrasion from use, cleaning, and the elements.

[0130] The invention will now be further illustrated with reference tothe following examples without the intention to limit the inventionthereto. All parts and percentages are by weight unless statedotherwise.

EXAMPLES

[0131] TABLE 1 Designation Material Availability/Preparation APTES3-aminopropyltriethoxysilane; Sigma-Aldrich, Milwaukee, WINH₂(CH₂)₃Si(OC₂H₅)₃ APTMS 3-aminopropyltrimethoxysilane; Sigma-AldrichNH₂(CH₂)₃Si(OCH₃)₃ BO 2-Butanone oxime; Sigma-Aldrich CH₃CH₂C(═NOH)CH₃Ethyl acetate CH₃CO₂C₂H₅ Sigma-Aldrich DBTDL Dibutyltin dilaurate;Sigma-Aldrich [CH₃(CH₂)₃]Sn[CO₂(CH₂)₁₀CH₃]₂ MeFBSEN-methylperfluorobutanesulfonyl Made by reacting ethanol;C₄F₉SO₂N(CH₃)CH₂CH₂OH perfluorobutanesulfonyl fluoride with CH₃NH₂ andethylene chiorohydrin, essentially as described in Ex. 1 of U.S. Pat.No. 2,803,656 (Ahlbrecht, et al.) MIBK Methylisobutyl ketone;Sigma-Aldrich (CH₃)₂CHCH₂C(O)CH₃ MPEG 350 CARBOWAX ™ 350; Union Carbide,Danbury, CT Methoxypolyethylene glycol (MW_(av) = 350) MPEG 550CARBOWAX ™ 550; Union Carbide, Danbury, CT Methoxypolyethylene glycol(MW_(av) = 550) MPEG 750 CARBOWAX ™ 750; Union Carbide, Danbury, CTMethoxypolyethylene glycol (MW_(av) = 750) MPEG 2000 CARBOWAX ™ 2000;Union Carbide, Danbury, CT Methoxypolyethylene glycol (MW_(av) = 2000)N100 DESMODUR ™ N-100; eq wt = 191 Bayer Polyfunctional isocyanate resinbased on hexamethylene diisocyante N3300 DESMODUR ™ N-3300; eq wt = 194Bayer, Pittsburgh, PA Polyfunctional isocyanate resin based onhexamethylene diisocyanate PEG 1000 CARBOWAX ™ 1000; Union CarbidePolyethylene glycol (MW_(av) = 1000) PEG 1450 CARBOWAX ® 1450; UnionCarbide Polyethylene glycol (MW_(av) = 1450) PEG 3350 CARBOWAX ™ 3350;Union Carbide Polyethylene glycol (MW_(av) = 3350) FC-672 Acrylate StainBlocker Minnesota Mining and Manufacturing, St Paul, MN

Fabrics

[0132] Fabrics tested included: 65/35 polyester/cotton woven twill (8ounces/yd² basis wt; available from Avondale Mills, Graniteville, S.C.),50/50 polyester/cotton plain weave (6 ounces/yd² basis wt; availablefrom Reeves Brothers Inc., Spartanburg, S.C.), and 60/40cotton/polyester pique knit (5 ounces/yd² basis wt; available fromCleveland Mills, Lawndale, N.C.).

[0133] Application & Testing of Compositions

[0134] Application of compositions to polyester/cotton woven fabrics

[0135] A 65% polyester, 35% cotton twill fabric was dipped into a bathof the diluted polymer and immediately sent through a nip. Theconcentration of the bath is adjusted to produce a fabric that when dryhad a fluorochemical solids coating ranging from 0.2 to 0.45% solids ofthe fabric total weight. The bath also contained a glyoxal-type resin,PERMAFRESH™ ULF (Omnova Solutions, Inc., Chester, S.C.) at about 10% onthe weight of the bath, a citric acid activated magnesium chloridecatalyst, CATALYST™ 531 (Omnova Solutions, Inc.) at about 2.5% on theweight of the bath, and a nonionic surfactant, PAT-WET™ LF-55 (YorkshirePat-Chem Inc., Greenville, S.C.), at about 0.1% on the weight of thebath. The fabric was dried and cured for 10 minutes at 150° C. Variousperformance tests were run on the fabric.

[0136] Application of compositions to Cotton/polyester knit fabric

[0137] Knit fabrics were treated in the same way as the woven fabrics,with the exception that FREEREZ™ 845 (Noveon, Inc., Cleveland, Ohio), apre-catalyzed glyoxal-type resin was used in place of the resin andcatalyst combination above at about 12% on the weight of the bath.

[0138] Performance Test—Oil Repellency

[0139] This test measures the resistance of the treated fabric tooil-based insults. A drop of one standard surface tension fluid (of aseries of 8, with decreasing surface tensions) is dropped on a treatedfabric. If after thirty seconds there is no wetting, the next higheststandard number fluid (next lowest surface tension) is tested. When thelowest number fluid soaks into the fabric, the next lower number is therating. For example, the fabric will receive a three rating, if thenumber four fluid wets the fabric. A more detailed description of thetest is written in the 3M Protective Material Division's “Oil RepellencyTest I” method (Document # 98-0212-0719-0).

[0140] Performance Test—Water Repellency:

[0141] This test measures the resistance of the treated fibroussubstrates to water based challenges. A drop of one standard surfacetension fluid (of a series of 11, with decreasing surface tensions,based on water and water/isopropyl alcohol mixtures where 100% water isa 0 rating and 100% IPA is a 10 rating ) is placed on a treated fabricto form a bead. If after thirty seconds there is no wetting, the nexthighest standard number fluid (next lowest surface tension) is tested.When the lowest number fluid soaks into the fabric, the next lowernumber is the rating. For example, the fabric will receive a threerating, if the number four fluid wets the fabric. A more detaileddescription of the test is written in the 3M Protective MaterialDivision's “Water Repellency Test II” method (Document #98-0212-0721-6).

[0142] Performance Test—Artificial Antisoiling

[0143] This test measures the resistance of the treated fibroussubstrates to water based challenges. Typically a 12 in by 18 in sampleof carpet is divided into three to six sections. One section is leftuntreated as the control and the other are treated with a protectivefinish and let dry at room temperature where T is=or<100 degrees F andreleative humidity is<50%. The treated article is afixed in a drumfilled with 40 ceramic pellets half weighing 10 g and half weighing 20 gand 20 g of 3M standard oily test soil (available from 3M ProtectiveMaterials Division Product 41-4201-6292-1). The drum is rolled for 10minutes and then rolled the other opposite direction for 10 minutes. Thecarpet is removed and vacuumed in two directions and the treated areasare compared with an untreated area. Direct comparisons are made withinthe same sample and are rated from 1 to 5 where 3 is untreated, 1 ismore soiled and 5 is no significant soiling. A more detailed descriptionof the test is written in the AATC “Artificial Antisoiling Test” method123-1995.

[0144] Performance Test—Acid Stain Resistance

[0145] This test measures the resistance of the treated fibroussubstrates to red acid dye stain. Test Method AATCC TM 175-1998 wasfollowed.

[0146] Performance Test—Oil Repellency—Durability

[0147] The Oil Repellency Test was run on treated fabric that hadsubsequently been washed for 5, 10, or 20, consecutive launderings,followed by tumble drying, as described in the 3M Protective MaterialsDivision “Laboratory Laundering Procedures” for home launderingsimulation (Document # 98-0212-0703-4).

[0148] Performance Test—Stain Release

[0149] This test evaluates the release of forced-in oil-based stainsfrom the treated fabric surface during simulated home laundering. Fivedrops of mineral oil, Stain K (Kaydol, Witco Chemical Co.) are droppedonto the fabric surface in a single puddle, and a separate puddle of 5drops of MAZOLA™ corn oil, Stain E, are dropped on the fabric, and in athird puddle, 5 drops of dirty motor oil (3M Co.) are dropped onto thefabric. The puddles are covered with glassine paper, and weighted with afive-pound weight each for 60 seconds. The weights and glassine paperare removed from the fabric. The fabric sample is hung for 15-60minutes, and then washed and dried. Samples are evaluated against arating board, and assigned a number from 1 to 8. An 8 represents totalremoval of the stain, where 1 is a very dark stain. A more detaileddescription of the test is written in the 3M Protective MaterialDivision's “Stain Release Test I” method (Document # 98-0212-0725-7).

[0150] Performance Test—Stain Release—Durability

[0151] The Stain Release Test was run on treated fabric that hadsubsequently been washed for, e.g., 5, 10, or 20, consecutivelaunderings, followed by tumble drying, as described in the 3MProtective Material Division's “Laboratory Laundering Procedures” forhome laundering simulation (Document # 98-0212-0703-4).

[0152] Performance Test—Fabric Absorbency

[0153] This test provides a rough index of fabric absorbency. A drop ofwater is placed on the fabric surface, and the amount of time it takesfor that drop to absorb into the fabric, leaving a matte, wet surface,is recorded. A more detailed description of the test is written in the3M Protective Material Division's “Fabric Absorbency Test” method(Document # 98-0212-0710-9). Absorbency time is also referred to as thewicking time. Wetting time is the time from application of the waterdrop, until the first evidence of darkening or wetting appears under thewater drop, was also recorded.

[0154] Preparation 1:

[0155] Fluorochemical urethane MeFBSE/N3300/PEG 1450/APTES A 1 literflask was charged with of MeFBSE (58.89 g), DBTDL (3 drops; ˜20 mg) andMIBK(237.0 g). The temperature of the stirred mixture was raised to 60°C. under a purge of dry nitrogen. N3300 (40.0 g) was then slowly added,maintaining the temperature between 60-65 C. Upon completion of theaddition, the reaction mixture was stirred for 1 hour at 60° C. APTES(4.56 g) was then added dropwise, keeping temperature of the reactionmixture below 65° C., and the reaction mixture was stirred for 30minutes. Solid PEG 1450 (14.95 g) was added to the stirred mixture, andthe reaction was followed to completion via FTIR, as determined bydisappearance of the —NCO band at approximately 2289 wavenumbers.

[0156] Emulsification: To this vigorously stirred organic mixture wasslowly added DI water ( 944 g; @ 60° C.). This pre-emulsion mixture wasthen sonicated for 2 minutes. A rotary evaporator connected to anaspirator was used to strip the MIBK from the mixture. The resultingemulsion was 20-30% solids.

[0157] The method described in Preparation 1 was followed to producePreparations 2-11 and Comparative Preparation C1, using equivalentweight ratios and substitutions of materials as listed in Table 2. TABLE2 Eq. Wt. Eq. Wt. of Eq. Wt. Preparation isocyanate Eq. Wt. ofaminosilane Eq. Wt. of glycol No. (type) MeFBSE (type) (type) 1 1.00(N3300) 0.80 0.10 (APTES) 0.10 (PEG 1450)  1a 1.00 (N3300) 0.80 0.10(APTMS) 0.10 (PEG 1450) 2 1.00 (N3300) 0.80 0.05 (APTES) 0.15 (PEG 1450)3 1.00 (N3300) 0.70 0.15 (APTES) 0.15 (PEG 1450) 4 1.00 (N100) 0.80 0.05(APTES) 0.15 (PEG 1450) 5 1.00 (N100) 0.80 0.10 (APTES) 0.10 (PEG 1450)6 1.00 (N3300) 0.80 0.075 (APTMS) 0.125 (PEG 1450)  2a 1.00 (N3300) 0.800.05 (APTMS) 0.15 (PEG 1450) C1 1.00 (N3300) 0.80 — 0.20 (PEG 1450) 71.00 (N3300) 0.80 0.05 (APTES) 0.15 (MPEG 350) 8 1.00 (N3300) 0.80 0.05(APTMS) 0.15 (MPEG 550) 9 1.00 (N3300) 0.80 0.05 (APTMS) 0.15 (PEG 1000)10  1.00 (N3300) 0.80 0.05 (APTMS) 0.15 (MPEG 2000) 11  1.00 (N3300)0.80 0.05 (APTMS) 0.15 (PEG 3350)

Testing on Carpet

[0158] preparations 1-11 and Comparative Preparation C1 were diluted toa 3% solids emulsion with DI water and applied to carpet as anaerosolized spray (Blue Transition III virgin carpet available from ShawIndustries, Dalton, Ga.) to net a 0.6 g/ft² solids add-on. Results ofstatic water repellency (Performance Test—Water Repellency), static oilrepellency (Performance Test—Oil Repellency), antisoiling (PerformanceTest—Anti-Soiling Resistance) and acid stain resistance testing(Performance Test—Acid Stain Resistance) for Examples C1-C11 are listedin Table 3. TABLE 3 Preparation Static Water Static Oil Anti- Acid StainEx No. Repellency Repellency soiling Resistance C1 C1 4 4 3.5 3.5 C2 1 45 4.5 3.5 C3 2 4 4 4 3.5 C4 3 3 3 3.5 3.5 C5 4 2 2 4 3 C6 5 2 2 4 3 C7 64 4 4.5 3.5 C8 7 3 3 4.5 3.5 C9 8 2 3 4.5 3.5 C10 9 3 3 4.5 3.5 C11 10 1 2 3.5 3.5 C12 11  DI Water 2 3 3.5 C14 C3 None None 3 1 (untreated)

[0159] Test on fabrics:

[0160] Preparations 1-11 and Comparative Preparation C1, were diluted to4% solids emulsion with DI water and applied to cotton/polyester 35/65blend fabric (#7206 from Test Fabrics Inc. Middlesex, N.J.) to yield a0.8 g/ft² add-on. TABLE 4 Static Water Static Oil Ex Preparation No.Repellency Repellency Antisoiling C15 C1 3 4 3.5 C16 1 3 4 4.5 C17 2 3 44 C18 3 1 4 3.5 C19 4 1 2 4 C20 5 1 2 4 C21 6 3 5 4.5 C23 untreated 0 01

[0161] Preparation 12:

[0162] Blocked isocyanate extender N100/MPEG 750/BO

[0163] A 1 liter flask, equipped with a reflux condenser, a mechanicalstirrer, thermocouple and nitrogen inlet was charged with N100 (95.5 g),ethyl acetate (250.0 g) and MPEG 750 (125.0 g). To this stirred mixturewas added DBTDL (0.25 g) and the ensuing mixture was heated to 75° C.and stirred overnight. The mixture was then cooled to room temperatureand BO (29.1 g) was added dropwise with stirring. The mixture was heatedto 75° C. and stirred overnight. DI water (750.0 g) was slowly added,allowing the temperature to be held between 65° C. and 75° C. duringaddition. The mixture was homogenized using an ultrasonic homogenizer(model CPX 600, available from Cole-Parmer, Vernon Hills, Ill.) for fiveminutes. Ethyl acetate was removed by distillation under reducedpressure. A hazy solution was obtained.

[0164] Preparations 13-15

[0165] The procedure outlined above for Preparation 12 was followed tomake Preparation 13-15, with substitution of materials as described inTable 5. TABLE 5 —NCO —OH BO Water Preparation % solids MPEG eqiv equivequiv equiv 13 31.1 550 1.00 0.33 0.67 0.00 14 30.5 750 1.00 0.33 0.380.29 15 31.7 2000 1.00 0.33 0.67 0.00

[0166] Table 5. Results of Preparations C1, 2 and 7 applied to 50/50polyester/cotton plain weave fabric TABLE 6 Pre- Solids Initial para- onOil Ex tion fiber repellency Wet Absorbency K E C C24 — — 0 0.5 30 5 5 3C25 2 0.20 6 23 30 6.5 6 5.5 C26 C1 0.19 6 15 30 7 6.5 6 C27 2a 0.22 624.3 30 6.5 7 6.5

[0167] Table 6. Results of Preparations C1, 2 and 8 applied to 50/50polyester cotton weave fabric; extended launderings (5, 10 and 20).TABLE 7 Ex O/R Wet Absorbency K E C 5 Launderings C24 0 0.5 6.3 5 5 3C25 3 13 30 6.5 6.5 5 C26 0 0.5 30 6.5 7 5 C27 3 18 30 6.5 6.5 6.5 10Launderings C24 0 0.5 6.7 5 5 3 C25 1.5 2.3 30 6 7 6 C26 0 0.5 30 6 6.55 C27 1.5 1.3 30 6.5 7 5 20 Launderings C24 0 0.5 5.1 5 5 3 C25 0.5 1.330 6.5 6 4 C26 0 0.5 23 6 6 5 C27 1 0.5 30 6.5 6 4

[0168] Tables 6 and 7, example C-26, shows that without the silane, nooil repellency is present at 5 launderings, where examples C-25 andC-27, with silane, show oil repellency durability to 20 launderings.Samples C-25 and C-27 show longer absorbency times than C-26. Longerabsorbency times are a measure of the resistance of the fabric towet-out by aqueous materials, e.g. water. In all examples, stain releasevalues were at least one point, or significantly better than, thecontrol example, C-24.

[0169] Table 8 Results of Preparation 7 (0.45% solids on fiber) withvarious extenders on 60/40 cotton/polyester pique knit fabric TABLE 8Ex- Initial C4 tender Absor- Ex Prep sof sof O/R Wet bency K E C C-28 —— — 0 0.5 0.5 5 6.5 3 C-29 2 0.453 4 1.7 30 7 7.5 6.5 1 2a & 13 0.4530.53 4.5 2.7 30 7 7.5 7.5 2a 2a & 14 0.453 0.52 4.5 6.7 30 7.5 8 7.5 32a & 15 0.453 0.54 5 2.8 30 7.5 8 7.5

[0170] Table 9. Results of Preparation 2 applied to 60/40cotton/polyester knit fabric; extended launderings (4, 8 and 12) TABLE 9Ex O/R Wet Absorbency K E C 4 Launderings C-28 0 0.5 0.5 5 6.5 3 C-29 01.1 30 6.5 7 6.5 1 0 2.2 30 7 7 7 2 0 1.2 27.1 7.5 7.5 7 3 0 1.3 30 7.57 7 8 Launderings C-28 0.5 0.5 5 6 3 C-29 0.5 30 6.5 7 6.5 1 1 30 6.5 76.5 2 1.2 27.8 7 7.5 7 3 0.5 5.8 6.5 7.5 6.5 12 Launderings C-28 0.5 0.55 6.5 3 C-29 0.5 30 6.5 6.5 5 1 0.5 30 6.5 6.5 6.5 2 0.5 30 7 7 6.5 30.5 5 7 7 6

[0171] Tables 8 & 9 show performance on a knitted substrate of thefluorinated compound alone, C-29, and the performance of the fluorinatedcompound with the various extender preparations, 1, 2, 3. In examples 1and 2, extenders with MPEG 550 and 750 respectively, extended both theabsorbency times, and the release of Stain C, to at least 12launderings. In example 3, use of an extender with MPEG 2000, improvedthe release of Stain C. Overall, stain release is shown to be improvedby treatment with the fluorinated and hydrocarbon extender incombination.

[0172] Table 10 Results of Preparation 1 applied at 0.29% solids onfiber to 65/35 Polyester/Cotton twill fabric with various extentenders.TABLE 10 Ex Preparation C4 sof Extender sof C-30 — — — C-31 1 0.289 — 41a & 13 0.289 0.44 5 1a & 14 0.289 0.43 6 1a & 15 0.289 0.45

[0173] Table 11 Results of Preparation 1 applied at 3% to 65/35Polyester/cotton twill fabric initial, 5 and 10 launderings TABLE 11Absor- Ex O/R Wet bency K E C Initial C-30 0 0.5 3.1 6 6 4 C-31 6 30 307 7 4 4 6 30 30 7.5 7.5 7 5 6 30 30 7.5 7 7 6 6 30 30 7.5 7.5 7 5Launderings C-30 0 0.5 0.5 6 6.5 4 C-31 5 30 30 7 6.5 3 4 5 30 30 7.5 76.5 5 4 30 30 7.5 7 6.5 6 2 10.8 30 7.5 7 7 10 Launderings C-30 0 0.50.5 6 6.5 4 C-31 4 30 30 7 6.5 3 4 3.5 30 30 7 7 5 5 2 30 30 7.5 7 6 61.5 1.9 30 7.5 7 6.5

[0174] Table 12. Results of Preparation 1 applied at 3% to 65/35Polyester/cotton twill fabric 20, 25 and 30 launderings TABLE 12 O/R WetAbsorbency K E C 20 Launderings C-30 0 0.5 0.5 6 6 4 C-31 2 11.1 30 7 73 4 2 2.3 30 6.5 7 6.5 5 1 9.2 30 7 7 6 6 0 0.5 11.7 7.5 7 7 25Launderings C-30 0 0.5 0.5 6 6.5 4 C-31 2 4.5 30 7 6.5 2.5 4 1.5 4.2 307 7 6 5 0.5 1.6 30 7 6.5 6 6 0 0.5 10.6 7.5 7.5 7 30 Launderings C-30 00.5 0.5 6 6.5 4 C-31 1.5 4.1 30 7 6.5 2.5 4 1 2.5 30 7 6.5 6 5 0.5 1.630 7 6.5 6 6 0 0.5 2.8 7.5 7.5 7

[0175] Tables 10, 11, and 12 demonstrate performance of the variouspreparations on yet another fabric, 65/35 polyester/cotton twill.Anti-absorbency benefits of extender preparations 13 and 14 are againdemonstrated in examples 4 and 5. All extender examples, 4, 5 and 6 showsignificant improvements in release of Stain C in as many as 30 homelaunderings. Again, on average, stain release is improved with thecombination of the hydrocarbon extender and fluorochemical compound.

[0176] Table 13 shows that curing compositions at ambient conditions (7)will provide stain release benefits to fabrics over controls (C-32,C-33). TABLE 13 Prepara- Cure Initial Ex tion C4 sof Extender sof TempO/R K E C C-32 — — — RT 0 6 6 4 C-33 — — — 300 F. 0 6 6 4 7 6 & 15 0.560.16 RT 0 6.5 7 6 8 6 & 15 0.56 0.16 150 F. 1 7 7 6 9 6 & 15 0.56 0.16200 F. 5 7 8 6.5 10 6 & 15 0.56 0.16 250 F. 5 7.5 7.5 7 11 6 & 15 0.560.16 300 F. 5 7 7.5 7.5

What is claimed is:
 1. A chemical composition comprising: (a) a firstcomponent comprising one or more urethane comprising the reactionproduct of: (1) one or more polyfunctional isocyanate compounds; (2) oneor more hydrophilic polyoxyalkylene compounds; (3) one or more silanecompounds of the formula: X—R¹—Si—(Y)₃  wherein X is —NH₂; —SH; —OH;—N═C═O; or —NRH where R is selected from the group consisting of phenyl,straight and branched aliphatic, alicyclic, and aliphatic ester groups;R¹ is an alkylene, heteroalkylene, aralkylene, or heteroaralkylenegroup; and each Y is independently a hydroxyl; a hydrolyzable moietyselected from the group consisting of alkoxy, acyloxy, heteroalkyoxy,heteroacyloxy, halo, and oxime; or a non-hydrolyzable moiety selectedfrom the group consisting of phenyl, alicyclic, straight-chainaliphatic, and branched-chain aliphatic, wherein at least one Y is ahydrolyzable moiety; and (4) one or more fluorochemical monofunctionalcompound; and (b) a second component comprising one or more hydrophilicauxiliary compounds capable of further improving the oil- and/or waterrepellency or soil/stain release properties of a fibrous substratetreated with the fluorochemical urethane compounds.
 2. The chemicalcomposition of claim 1 wherein the polyfunctional isocyanate compound ofsaid first component is a diisocyanate or triisocyanate.
 3. The chemicalcomposition of claim 1 wherein the fluorochemical monofunctionalcompound of said first component is of the formula: R_(f)—Z—R²—Xwherein: R_(f) is a perfluoroalkyl group or a perfluoroheteroalkylgroup; Z is a connecting group selected from a covalent bond, asulfonamido group, a carboxamido group, a carboxyl group, or a sulfonylgroup; and R² is a divalent straight or branched chain alkylene,cycloalkylene, or heteroalkylene group of 1 to 14 carbon atoms; and X is—NH₂; —SH; —OH; —N═C═O; or —NRH where R is selected from the groupconsisting of phenyl, straight and branched aliphatic, alicyclic, andaliphatic ester groups; R¹ is an alkylene, heteroalkylene, aralkylene,or heteroaralkylene group.
 4. The chemical composition of claim 3wherein R_(f) is a perfluoroalkyl group of 2 to 12 carbons.
 5. Thechemical composition of claim 3 wherein R_(f) is a perfluoroalkyl groupof 3 to 5 carbons.
 6. The composition of claim 1 wherein said firstcomponent polyoxyalkylene compounds are homo-and copolymers ofpolyoxyethylene and polyoxypropylene.
 7. The composition of claim 1wherein said second auxiliary component is the reaction product of apolyisocyanate, a blocking agent and a polyoxyalkylene compound.
 8. Thecomposition of claim 7 wherein said isocyanate groups of said secondcomponent polyisocyanate are blocked isocyanate groups.
 9. Thecomposition of claim 8 wherein said blocked isocyanate groups areprepared by a thermally reversible reaction with phenols, lactams, andoximes.
 10. The composition of claim 7 wherein said polyoxyalkylenecompounds of said second component are homo- and copolymers ofpolyoxyethylene, polyoxypropylene, polyoxytetramethylene.
 11. Thecomposition of claim 1 wherein the amount of said hydrophilicpolyoxyalkylene compounds of said first component is sufficient to reactwith between 0.1 and 30% of available isocyanate groups, the amount ofsaid silane compounds is sufficient to react with between 0.1 and 25% ofavailable isocyanate groups, and the amount of said fluorochemicalmonofunctional compounds is sufficient to react with between 60 and 90%of available isocyanate groups of said urethane compounds.
 12. Thecomposition of claim 1 wherein the amount of said polyoxyalkylenecompound of said second component is such that from about 25 to about75% of the available isocyanate groups of said auxiliary compound arereacted.
 13. The composition of claim 12 wherein the unreactedisocyanate groups are blocked isocyanate groups.
 14. The composition ofclaim 1 wherein the ratio of said first component urethane compound tosaid second auxiliary compound is from 12:1 to 1:12.
 15. The compositionof claim 1 wherein the ratio of said first component urethane compoundto said second auxiliary compound is from 3:1 to 6:1.
 16. Thecomposition of claim 1 wherein said polyoxyalkylene compound of saidfirst component has a functionality of greater than
 1. 17. Thecomposition of claim 7 wherein said polyoxyalkylene compound of saidsecond component has a functionality of one.
 18. A treatment compositioncomprising a solution of the chemical composition of claim 1 and asolvent.
 19. The treatment composition of claim 18 wherein the solventis selected from the group consisting of water, an organic solvent, andmixtures thereof.
 20. The treatment composition of claim 18 comprisingfrom about 0.1 to about 50 percent chemical composition.
 21. An articlecomprising a substrate having a cured coating derived from at least onesolvent and a chemical composition of claim
 1. 22. The article of claim21 wherein said substrate is a fibrous substrate.
 23. A method forimparting stain-release characteristics to a substrate comprising thesteps of applying the treatment composition of claim 1, and allowing thecoating composition to cure.
 24. The method of claim 23 wherein saidsubstrate is a fibrous substrate
 25. The method of claim 24 wherein saidcoating composition is applied in an amount sufficient to providebetween 0.05% and 5% solids on fiber.
 26. The method of claim 24 whereinsaid composition is cured at ambient temperature.
 27. A method forimparting stain-release characteristics to a fibrous substratecomprising the steps of: (a) applying a coating composition of claim 13,and. (b) curing the coating composition at elevated temperature todeblock said blocked isocyanate groups.